Aldehyde-free alcoholic liquids



Dec. 16,1930. ||t H EUSER 1,785,447

ALDEHYDE FREE ALCOHOLIC LIQUIDS 'n Filed June 28, 1926 Patented Dec. 16 1930 UNITED STATES HERMAN HEUSER, OF CHICAGO, ILLINOIS ALDEHYDE-FREE 4.ALGOIIOLICl LIQUIDS Application led June.28,

The present invention relates to the product-ion of liquids containing ethyl alcohol derived by fermentation and which are free V from aldehydes as well as from fusel oil and other toxic products of fermentation. Thus, my invention may be employed for the production of fermented'malt liquids of the tonic or medicinal type as well as of fermented fruit juice liquids when the Amanufacture thereof is permissible for sacramental, me

dicinal or other purposes Aor as anl intermediate for the manufacture of other material.

Theinvention will be fully understood from. the following description, illustrated by the accompanying drawing, in which apparatus suitable for carrying theinvention into effect is diagrammatically illustrated, partly in section, c

In the manufacture of liquids of the type described above, and containing alcohol, it has not hitherto been recognized that the toxicity ordinarily ascribed to the alcoholy is dueto fusel oils and especially to 'aldehydes' and like oxidized products, and that the same also have a distinctly deleterious effect on other characteristics of the liquid I have found that these accompanying materials are very toxic, vparticularly the aldehydes, the toxicity of which is apparently enhanced by their volatility and peculiar chemical reactivity. The absence of the toxic substance entirely deprives the material of physiological toxicity, even with pure ethyl alcohol present in proportions as high as 3 to 6%. Furthermore, I have found that Acertain of the deleterious physiological effects, as well as other characteristics hitherto regarded as due solely to the alcohol present in liquids,

40 particularly when in small proportions, are

in fact due to the presence of aldehydes which I have found, by careful research and by the development of sensitive, accurate analytical tests, to be present in all alcoholic liquids including chemically pure alcohol as hitherto produced. The aldehydes may be formed during the manufacture of the liquid or by subsequent oxidation (as by surface contact with air), and in aqueous solutions of alcoholas well as in other alcoholic liquids pro- 1926. Serial No. 119,057.

duced by fermentation or lby subsequent distillation. y

By methods which I have 'discovered and which are fully set forthl hereinafter, I have been able to produce and to retain in markety able form liquids containing alcohol and free, not Aonly of fusel oil, but also of'aldehydes, and hence free from toxic and intoxicatlng effect hitherto regarded as necessarily present in such material. My process and products are of particular value when the liquids are employed medicinally, owing to the absence of the toxic action of the aldehydes, etc., normally present.

In the following description of my 1nVen` tion, I have set forth a particular embodiment of apparatus and have, for convenience `in description, referred to a fermented maltcereal liquid of suitable extract percentage, as the initial material.. It will be readily understood that other apparatus may be employed and lthat such materials may be einployed, as, for example, a fermented fruit' juice, or'a distilled and diluted product intended for medicinal purposes. The initial material employed-may be considered as containing 5% of alcohol by volume and the legally required yextract percentage in the specific lexample set forth.

Referring to the drawing, the numeral 5 designates a kettle, shown partially in section` provided in its base with a steam-jacket 6. The upper portion of the kettle is suitably domed, as at 7, and is provided with a vaporoutlet pipe 8, which may suitably lead to a condenser or open directly into the atmosphere, as desired. The vapor-outlet pipe 8 is suitably of goose-neck type, and the upper portion of the kettle 5, the dome 7, and the portion of the vapor-outlet pipe 8 from which condensate, if formed, may run back into the kettle are provided with lagging or thermal insulation of any suitable effective type, asindicated at 9, for the purpose of preventing condensation as hereinafter more fully set 95 forth. The kettle is suitably provided with a manhole 10, a liquid gauge 11 and a thermometer 12together with any other desired control and inspection devices. In the lower portion of the kettle there is provided a stirrer 13 mounted on a-vertical shaft 14A which passes through a suitable,- s tuing box 15 in the bottom of the kettle-, the shaft 14 beingdriven in any suitable manner, for example, by motor 16 throughspeed reducer 17 andthe gearing 18. The pipe 19 provided with valve 2O serves as an inlet to the interior of thekettle 5. The contents thereofl may charged through the pipe 26 to the kettle 28, the valve 24, in the line 23'is closed.

In the flow of the liquid to the kan@ 2a,

- it passes through the pipe 26 into the pipe 29 leading-into the bottom of the'kettle, the

latter pipe being provided with valve 30. A branch pipe 31 provided with valve 32 also connects with the pipe 29, so that the contents of the kettle'28 may be discharged through the pipes 29 and 31 from the system.

The kettle 28 is in form generally similar to the kettle 5 already described, being provided in its base with a jacket 33 to which steam may be supplied through a valved pipe 34. The kettle 28 is likewise provided around its side walls with a jacket 35, which does not communicate `with the jacket 33, and to whlch water or other suitable cooling medium may be supplied through the valved pipe'36, making its exit through the pipe 37. The upper. portion of the kettle. 28 is domed, as at 39, and is provided with a vapor pipe 40, a valve `4l .of gate or other suitable type being providedm the outlet pipe 40 as close to the top shaft 47 which passes through a stuiiingbox of the kettle as is practicable. To prevent condensation, the upper portion of the kettle and the vapor-outlet pipe are lagged with any suitable thermal insulation, as indicated at 42. The kettle 28 is provided with any desired control and observation devices, for example, thermometer 43, liquid gauge 44 and pressure gauge 45.l

In the lower portion of the kettle 28 there is provided a stlrrer 46, similar to the stirrer 13 provided in the kettle 5. The stirrer 36 is suitably mounted upon a rotatable vertical 48.in the bottom of the kettle, and is driven lby any suitable device, for example, by the motor 49 through the speed reducer 50 and the gearing 51. Within the kettle 28 there are likewise provided a series of coils 52, to which brine or other suitable cooling medium may be supplied .through the inlet pipe 53., provided with valve 54.' The cooling medium may make its exit from the coils .52 through the outlet pipe 55. ,A pipe 56, leading from any suitable source of carbon-dioxide under pressure, divides into two branches 57 and 58, the former leading to the upper portion 'of the kettle 28 and the latter into the ket-v tle at its bottom. The line. 57 is provided with a control valve 59 and a check valve 60. The line 58 is provided with a control valve 61 and acheck valve- 62. A vent 63 controlled by a valve is provided in the upper portion of the kettle. Samples ofthe contents of the kettle may be removed through the sampling cock 64.

In. order that the invention may be cleari ly understood, it will bev described in connection with the treatment of a specific maaterial, which may be, for example, a fermented liquid of the malt-cereal type containing initially about 5% 'of alcohol by volume and the necessary extract percentage. In starting operations, the fermented liquid is run into kettles 5 and 28, which are-of substantially equal capacity, until they are eacha little more than half full. capacity-of each of the kettles is 200 barrels, 105 barrels may be runinto each. The stir- 'rers 13 and 46 in the two kettles are then Thus, if the onv started in operation and the liquid in each kettle isheatedto boiling by supplying steam to the jackets in the bottoms of the kettles. The gateY valve 41 of kettle 28 is kept open. Assuming that the liquid employed has an alcohol content of 5% by volume, it will begin boiling at 95.8 C. The kettles being only a little more than half full, ample room is provided for the foam formed at the beginning of boiling. Boiling is continued until the vapors given 0H from the liquid are free from the characteristic fusel oil odor, which is present in them in the beginning of the op-v eration. In the specic instance cited, the li uid is entirely free from fusel oil and from al ehydes when it has been reduced to an alcohol content of 3.50% by Volume, at which point its boiling point at the altitude of Chicago is 97 C. The volume of the liquid at this point is reduced to about 100 barrels in a each kettle at the boiling temperature, corresponding to about 95.7 barrels of cold liquid in each kettle, 8.86% of liquid having been evaporated. i y' Vhen the point is reached at whichv the fusel oil and aldehyde 'is removed'as above 27 in the line 26 and the valve 30 in the line 39 are opened, and the entire body of liquid residue from the kettle 5 is discharged into the kettle 28. The flow of residue continues until the level of liquid in the kettle 28 reaches the gate valve 41, which point can be readily observed by means of the gauge 44. The valve 41 is then closed tightly, so that the kettle 28 is entirely filled with residue which is entirely freed of fusel oil andaldehydes and Which contains no air or oxygen. At this stage the alcohol content of the residue is about 3.25 to 3.5% by volume.

The residue inthe kettle 28 is' then cooled preferably, first by passing cold Water through inlet pipe 36 to and through the jacket 35 around the kettle and out through the youtlet pipe 37. When the residue has been partially cooled, for example, to about 32 C. the flow of Water through the cooling jacket 35 is stopped, it is preferably dra-ined, and the cooling is continue-d by flowing cold brine through inlet pipe 53, coils 52 within the tank and out of the outlet pipe 55. It is thereby brought to a temperature of 2 C. or lower when cooling is stopped. The volume of residue is reduced by cooling from 200 barrels hot residue to somewhat more than 191 barrelsA cold residue, the contraction being noted on the liquid gauge 44. In the operation as described, the spacev in the kettle above the cooled residue is highly evacuated it being understood that if the kettle has not suiicient'strength to withstand the strains set up by cooling, a gas completely free from oxygen, such as carbon-dioxide or nitrogen previously passed through an active oxygen absorbing medium, may be permitted to enter the t'op of the kettle, for example, through the line 57, during the cooling operation. No oxygen is permitted to come in contact with the surface of the cooling liquid for I have discovered that if the residue is cooled in the presence of an oxygen containing gas, up

to 0.40% by volume of oxygen is dissolved and there 1s a substantial oxidation of the alcohol content to aldehydes, readily notice;

able by the strong characteristic odor of a sample taken from the sampling cock 64. After the residue has cooled, any vacuumv filtering, bottling and pasteurizing in thef bottles. Other trade packages may be emhypoplhosphite may beso added per barrel of the liquid.

If desired, instead of carbonating in the usual manner, theV cooled liquid may -be carbonated in the kettle 28 in bulk. After the liquid has been cooled to the desired low temperature, as set forth above, the rotation of the stirrer 4 6 is continued, for example, at a rate of 60 to 65 revolutions per minute, and the carbon-dioxide is allowed to enter the chamber from the line 56 through line 5,8, valve 6l and valve 62. The pressure within the kettle gradually rises until a pressure slightly under that of the source of carbondioxide is reached. In order to continue the flow of the carbon-dioxide, the vent 63 may be slightly opened at this point, a small amount of carbon-dioxide permitted to es# cape and a continuous iowJof the carbon-dioxide into the beverage produced. After the liquid has been carbonated, it may be packaged in any suitable manner in use in the trade, the same precautions being taken to avoid acess of oxygen; containing gas or air as has been previously'mentioned.VY

The heating or boiling of fermented worts and similar liquids in the ordinary manner imparts tiereto a burnt or empyreumatic taste and odor; but by operating in accordance wii 'i my invention in which air is not permitted'access nor contact with the liquid or residue, this burnt taste and odor is yliquid from the kettle 5, when completely deprived of the fusel oil and aldehydes present thereih, may be discharged through the lines 2l and 23 through the cooler 25, the line having previously been freed from air or oxygen containing gas either by flowing an air-free liquid therethrough or by passing an air-free gas, such as carbon--dioxide therethrough. During the time that any liquid remains in the kettle 5, it must be kept at or sufficiently. near the'boiling point, so that air Will not be permitted access to the liquid and absence of aldehyde vformation in the liquid and return thereto assured.

- I have found that ingeneral the desired expulsion of fusel oil and aldehydes from a fermented liquid of the character above `referred to, containing,'for example, 3 to 7 alcohol and the permissible percentage of extract may be affected by continuing the boiling or evaporation until 25 to 40% of the Y alcohol (by volume) has been removed'. 1f

desired,the alcohol content of the residue may be supplemented by the addition thereto of an aldehyde-free ethyl alcohol solution in water. vOrdinary commercial ethyl alcohol or4 solutions containing it cannot be employed, as 'even when prepared under the most careful conditions as hitherto known, they contain detectable: quantities of aldehydes capable of substantially 'affecting the toxicity and intoxicating action of the liquid. I prefer, therefore, to prepare a solution of ethyl alcohol free from aldehyde, using the procedure above set forth in connection with the manufacture of the aldehyde' and fusel oil free residue from fermented liquids. In place of charging the kettles 5 and 28 with fermented liquid, as hereinbefore set forth.. they may be charged with an aqueous solution of chemically pure alcohol containing, sayl 5 to 50% alcohol and the operation conducted in exactly the manner above set forth. An aldehyde-free alcohol solution containing 4% alcohol, or-higher, depending upon the strength ofthe alcohol solution originally taken, may thus be produced and is found to differ markedly from a solution of alcohol made in the ordinary manner being entirely free from any odor or the usual alcohol sweetness. It is apparent that 4a sample of this liquid mustbe tested or examined at once upon withdrawal, as there is a rapid absorption of oxygen with a formation of quantities of aldehyde which appreciably affects the taste and 'order of the liquid and are qualitatively and quantitatively detectable by sensitive methods of analysis. If it is desired that the liquid shall retainits characteristics of absence of aldehyde taste and flavor and the absence resulting therefrom, it must be retainedl in containers from which air or other oxygen containing gases are excluded unless the ethyl found that, with reductio n in pressure, it is necessary to cause a greater proportienal evaporation of the alcohol (and hence of the liquid) than under atmospheric pressure to eHect the removal of the fusel oil. Further# more, in operating in vacuo and in the subsequent handling of the liquid Iy have found that there is much greater difficulty in secur ing freedom from aldehydes.

This application is in part a continuation discharging the residue at boiling temperature into a chamber, completely filling the 'I latter chamber with said residue at boiling temperature, sealing the chamber, and cooling the residue.

2. The method of producing an alcohol containing liquid free from fusel oil and aldehyde, which comprises boiling an alcoholic liquid in which fusel oil or aldehydes are present to remove therefrom as vapors a portion of its alcoholic content suiiicient to carry ofl" also the fusel voil and aldehyde present, and separating said vapors from the residue, completely filling a container with such residue while at boiling temperature, sealing the container and cooling the residue therein,

3. The' method of producing an f alcohol containing liquid free from fusel oiland aldehyde, which comprises heating an'alcoholic liquidin whichV .fusel oil or aldehydes are present to cause evaporation thereof unf' til the fusel oil and aldehyde have'been re.- moved as vapors, separating the vapors from the residue, a portion of its alcohol remaining therein, and thereupon cooling the alcoholic residue'liquid in the absence of air or gen. v

4. The method of producin an alcohol containing liquid free from usel' oil vand aldehyde, which comprisesevaporating an alcoholic liquid in which fusel oil or aldehydes are present, until the fusel oil and aldehyde have been removed, as vapors, and separating such vapors and accompanying vapor materials from the residue, maintaining a bdy of the residue in an open vessel whilel heating the same sufficiently to prevent access of air and aldehyde formation, and withdrawing residue from said heated body and cooling the withdrawn residue.

5. The method of producing any alcohol containing liquid free. from fusel oil .and

aldehyde, which comprises boiling Van alcol'V holic liquid in which fusel'ilorcaldehydes are present to remove therefrom' as vapor l a portion of its-alcoholic content sufficient to carry of also fusel oil and aldehyde present, separating from the alcohol-containing residue the removed alcoholic and.. accom-l panying vapors, completely filling a con'L tainer with such residue while at boiling teml perature, sealing the containerand'cooling the residue' therein, andA 'permitting 'an 'oxy gen free gas to enter the space Within said chamber formed by reduction of volume of the residue on cooling.A i

6. The method of producing an alcoholic liquid free from fuseloil and free from aldehyde, which comprises boiling a ferment-ed cereal liquid containing initially about 5% alcohol by volume to reduce its alcohol content to about 3.50% by volume, thereby removing fusel oil and aldehyde therefrom, v

accompanying vapor materials from the resi- A due, charging such residue While at boiling temperature into a container to completely fill the latter, sealing the container, and cooling it in the sealed container While permitting airffree gas to enter the space left by the residue on cooling.

8. The method of producing an alcoholic li uid free from fusel oil and freefrom alde 1yde,which comprises boiling a-fermented cereal liquid containing initially about 5% alcohol by volume, to reduce its .alcohol content to about 3.50% by volume, thereby removing fusel oil and aldehyde therefrom, as vapors and separating such vapors and accompanying vapor materials from the residue, charging such residue While at boiling temperature into a container to completely 'fill the latter, sealing the container,-

as vapors and separating such vapors andaccompanymg vapor materials from the residue, charging such residue While at boiling temperature into a container to completely fill the latter, sealing the container, and cooling it in the sealed container, forcing a continuous stream of carbon-dioxide into the cooled residue, While vigorously agitating the same, and venting excess carbon-dioxide from the container.

10.v The method of producing'a cereal y oxygen or air.

liquid of reduced alcohol content, free from burnt taste and flavor, which comprises boiling an alcohol-containing-beverage stock to vaporize a part of its alcohol together With its aldehydes, separating from the alcoholcontaining residue the evolved alcoholic and accompanying vapors, cooling the boiled beverage in the absence of air or oxygen and thereupon carbonating and filtering it.

11. The method of producing an aldehydefree liquid from an alcoholic. liquid in which fusel oil or aldehydes are present which comprises charging a portion of suchrliquid into a closed chamber, heating it therein to evaporate and remove therefrom its entire aldehyde contents together With a portion of its alcoholic contents, similarly heating a second portion of said liquid in a second chamber, discharging the aldehyde-free residue from i the second chamber, While boiling, into the 85 first chamber to vcompletely fill the latter, sealing the first chamber, While its contents are at boiling temperature, and subsequently cooling its contents.A

12. The method of producing an aldehydefree liquid froman alcoholic liquid in Which fusel oil or aldehydes are present which comprises charging a portion of such liquid into a vclosed chamber, heating it therein to evaporate and remove therefrom its entire aldehyde eontentsto'gether with a portion of its alcoholic contents, similarly'heating a second portion of said 'liquidin a second chamber,l discharging the aldehyde-free residue from the second chamber While boiling into the first chamber to completely fill the latter, sealing the first chamber While its contents are at boiling temperature, subsequent-ly vcooling its contents, and permitting an oxygen-free gas to' enter the space formed by contraction 0f the contents of the chamber 13. In the manufacture of alcohol-contain ing liquids from alcohol-containing,"stoc the steps of boiling the stock and' separatifnofl from the residue the evolved vapqrs contain?y 110 ing aldehydes and part of the alcfloljbf thg stock, and thereupon cooling the `boiled residue Without access to. or absorption ,incurranl HnUsER 

